2,9-Diazadibenzoperylene and 2,9-Dimethyldibenzoperylene-1,3,8,10-tetratriflates: Key to Functionalized 2,9-Diazaperopyrenes.

Abstract

The synthesis of 2,9‐diaza‐1,3,8,10‐tetratriflato‐dibenzoperylene (DDP 3 a) and corresponding 2,9‐dimethyl‐1,3,8,10‐tetratriflato‐dibenzoperylene (DBP 3 b) has been developed at multigram scale via reduction of one of the industrially most important high‐performance dyes, perylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9‐diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O‐phosphanyl substituents. The influence of electron‐donating substituents (OSiMe3, OPt‐Bu2, N‐piperidinyl), electron‐withdrawing (OTf, 3,5‐bis‐trifluoromethyl‐phenyl), and of electron‐rich π‐conjugated (2‐thienyl, 4‐tert‐butylphenyl, trimethylsilyl‐ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD‐DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI.